Imidoyl Chlorides Research Articles

Convenient Synthesis of Structurally Novel 1,3‐Disubstituted Azetidine Derivatives

A convenient synthesis of structurally novel 1,3‐disubstituted azetidine derivatives is described. The approach involves condensation of an azetidine building block with sulfonylated carbamic acid methyl ester, subsequently followed by quenching the imidoyl chloride with amines. Different derivatives were prepared by substituting benzhydrol as well as benzenesulfonamide as part of the core structure.

Palladium-Catalyzed Carbonylative 3-Component Synthesis of Quinazolinones

Reported is a Pd-catalyzed 3-component synthesis of quinazolinones from o-iodo­anilines, carbon monoxide, and imidoyl chlorides. Optimization studies using a variety of palladium sources and mono- and bidentate phosphorus ligands showed Pd(OAc)2/PPh3 to be the best combination for highest yields. In terms of reaction scope, substituents (EWGs and EDGs) on the 4-position of o-iodoanilines give competent yields (66-74%) but lower than when no substituted o-iodoaniline was involved (91%). Aryl and alkyl groups on the N,C sides of imidoyl chlorides gave medium to excellent yields. But when electron-poor substituents (e.g., 2-furanoyl) were involved, higher temperature (150 ºC) or longer reaction time (72 h) might be needed. The scope of the reaction was modestly studied.

Design, synthesis, and antimicrobial activity of fused triheterocyclic nitrogen systems involving tetrazolo[1,5-b][1,2,4]triazines [1

Dehydrogenative cyclization of the 6-substituted 7-arylidenehydrazinotetrazolo[1,5-b][1,2,4]triazines derived from 6-methyl and 6-phenyl derivatives of 7-hydrazinotetrazolo[1,5-b][1,2,4]triazines and aromatic aldehydes gave the corresponding 6-substituted 9-aryl-[1,2,4]triazolo[4,3-d]tetrazolo-[1,5-b][1,2,4]triazines. The latter compounds were also obtained by an alternative route involving dehydrative cyclization of 6-methyl and 6-phenyl derivatives of 7-chlorotetrazolo[1,5-b][1,2,4]triazines with aromatic hydrazides through the isolable aroylhydrazino intermediates. Also, the triazolotetrazolotriazine rings were accomplished by one-pot cyclization of cyclic amidrazones with aromatic acid chlorides. The ditetrazolo[1,5-b:1′,5′-d][1,2,4]triazine systems were synthesized by cyclization of the former cyclic amidrazones with nitrous acid, or cyclic imidoyl chlorides with sodium azide. The bis-triazolotetrazolotriazine derivatives were synthesized by cyclization of two equivalents of each cyclic imidoyl chloride with acid dihydrazides through the isolable bis-hydrazide products. The antimicrobial activity of representative compounds was studied.

Microwave-assisted multi-step synthesis of novel pyrrolo-[3,2- c]quinoline derivatives

A new approach for the synthesis of original substituted pyrrolo-[3,2- c]quinoline derivatives using microwave-assisted chemistry is described. The use of microwave activation in this synthesis resulted in high yielding and clean steps. The key step for introducing diversity is the amination or the Pd-catalyzed cross-coupling of an imidoyl chloride derivative, obtained in a straightforward manner and in good yield.

ChemInform Abstract: Enantioselective Organocatalytic Substitution of α‐Cyanoacetates on Imidoyl Chlorides — Synthesis of Optically Active Ketimines.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

A Precursor Route to Supramolecular Oligo(p‐phenylene terephthalamide) Block Copolymers

AbstractNew soluble precursors for the step‐wise synthesis of oligo(p‐phenylene terephthalamide) block copolymers are described. Kevlar‐like aramide oligomers up to the hexamer (six phenyl groups) were prepared in a polymer‐analogous manner. Activating the carboxylic‐acid‐carrying oligomers as carbonyl chlorides while reversibly transforming the aromatic amides into imidoyl chlorides gave access to soluble precursors. The dimer and tetramer precursor were prepared and used in block copolymer synthesis. Single‐crystal XRD confirmed the structure of the dimer precursor. Above a critical rod length, the Kevlar‐like rod‐coil block copolymers show strong aggregation in non‐polar solvents such as chloroform.magnified image

Palladium-Catalyzed Cyclocarbonylation of o-Iodoanilines with Imidoyl Chlorides to Produce Quinazolin-4(3H)-ones

A wide variety of substituted quinazolin-4(3H)-ones were prepared in 63-91% yields by the palladium-catalyzed cyclocarbonylation of o-iodoanilines with imidoyl chlorides and carbon monoxide. The reaction is believed to proceed via in situ formation of an amidine, followed by oxidative addition, CO insertion, and intramolecular cyclization to give the substituted quinazolin-4(3H)-ones.

ChemInform Abstract: Fluorinated N‐[2‐(Haloalkyl)phenyl]imidoyl Chloride, a Key Intermediate for the Synthesis of 2‐Fluoroalkyl Substituted Indole Derivatives via Grignard Cyclization Process.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Imidoyl Chlorides: New Promising Building Blocks in Synthesis of α-Aminophosphoryl Compounds

Synthetic and mechanistic aspects relevant to nucleo philic phosphorylation of imidoyl chlorides, their potentialities in preparing functionalized α-aminophosphoryl compounds were discussed.

Application of the aza-Wittig reaction to the synthesis of pyrazinothienotriazolopyrimidinones: a new tetracyclic ring system

A simple one-pot and efficient method is described for the synthesis of pyrazinothienopyrimidines 6 by domino processes involving aza-Wittig/intermolecular nucleophilic addition/intramolecular cyclization. A tandem aza-Wittig reaction of phosphazenes 7, derived from 6, with heterocumulenes (isocyanates, carbon disulfide or carbon dioxide) generates the pyrazinothienotriazolopyrimidinones 9, 11 and 12, respectively. Pyrazino[2′,3′:4,5]thieno[3,2- d]-1,2,4-triazolo[1,5- a]pyrimidin-4(3 H)-ones 15 and bis(pyrazinothienotriazolopyrimidinones) 17 were synthesized by the intermolecular aza-Wittig reaction of phosphazenes 7 with acyl chlorides or α,ω-dichlorides followed by heterocyclization via imidoyl chloride intermediate 16. Further S-alkylation of 11 and reaction of 6 with phosgeniminium chloride produce 2-alkylthio- and 2- N, N-dimethylaminopyrazinothienotriazolopyrimidinones 13 and 19, respectively.

Facile Synthesis of Fluorinated Purines and Thiapurines

The reaction of 2-(dialkylamino)-1,3-thiazol-4-amines and 1,2-dimethyl-1 H-imidazol-5-amine with aryl isocyanates, α-chloroalkyl isocyanates, N-(alkoxycarbonyl)imidoyl chlorides and 2,4,6-tris(trifluoromethyl)-1,3,5-triazine leads to thiapurines and purines containing trifluoromethyl groups in the 2- and 6-positions of the pyrimidine ring.

Facile Preparation of Polyfluoroalkylated Aldimines from Polyfluoroalkanoic Acids

Polyfluoroalkylated aldimines were prepared by reducing polyfluoroalkyl imidoyl chlorides, which are readily available from polyfluoroalkanoic acids, with LTBA (lithium tri-tert-butoxyaluminum hydride).

Fluorinated N-[2-(haloalkyl)phenyl]imidoyl chloride, a key intermediate for the synthesis of 2-fluoroalkyl substituted indole derivatives via Grignard cyclization process

Fluorinated N-[2-(haloalkyl)phenyl]imidoyl chloride, which was readily available from the corresponding anilines by using Uneyama's one-pot synthesis of fluorinated imidoyl chloride, was found to be a key intermediate for the facile synthesis of 2-fluoroalkyl substituted indole derivatives via the Grignard cyclization process. The bromination of 3-methyl group of 3-methyl-2-trifluoromethyl indole with NBS/CCl 4 led to the formation of 3-bromomethyl substituted indole which can be further utilized to synthesize some new and biologically interested indole derivatives.

Revisit to the reaction of [60]fullerene with nitrile ylides generated from imidoyl chlorides and triethylamine

The reaction of [60]fullerene (C 60) with nitrile ylides generated from N-benzyl-4-nitrobenzimidoyl chloride/ N-(4-chlorobenzyl)-4-nitrobenzimidoyl chloride and triethylamine gave only isomeric monoadducts of C 60 with [6,6]-closed structure. No [5,6]-open adduct of C 60 could be identified from these reactions. The previously reported [5,6]-open product of C 60 should be reassigned as a [6,6]-closed product.

Asymmetric Synthesis of New β,β-Difluorinated Cyclic Quaternary α-Amino Acid Derivatives

The synthesis of new β,β-difluorinated cyclic quaternary α-amino acid derivatives 1 in which a ring-closing metathesis reaction (RCM) constitutes the key step is described. The approach employs imidoyl chlorides 3 as fluorinated building blocks, and the overall process involves the stereoselective creation of a quaternary stereocenter. Complete selectivity was achieved when (R)-phenylglycinol methyl ether was used as chiral auxiliary, allowing for the preparation of new six-membered cyclic fluorinated α-amino acids as single enantiomers.

Synthesis of a new fluorinated oxazolidinone and its reactivity as a chiral auxiliary in Aldol reactions

A new enantiomerically pure fluorinated oxazolidinone has been prepared from a fluorinated imidoyl chloride and an optically pure sulfoxide. The diastereoselective reduction of the β-iminosulfoxide thus formed followed by elimination of the sulfoxide and cyclization of the created aminoalcohol furnishes the desired product. The fluorinated oxazolidinone was subsequently used as a chiral auxiliary in Aldol reactions. We also found that the selective formation of the syn-Evans and syn-non-Evans diastereoisomer can be controlled by adjusting the Lewis acid/base ratio.

A Novel Highly Stereoselective Synthesis of 2,3-Disubstituted 3H-Quinazoline-4-one Derivatives

[structure: see text]. An efficient three-step synthesis of chiral 3H-quinazoline-4-one derivatives from commercial materials is disclosed. The Mumm reaction of imidoyl chloride with alpha-amino acids followed by reductive cyclization affords enantiomerically pure (ee >93%) quinazoline-4-ones in good overall yield. A comparison with existing approaches indicates that this method is superior for hindered substrates.

Grignard Cyclization Reaction of Fluorinated N-Arylimidoyl Chlorides: A Novel and Facile Access to 2-Fluoroalkyl Indoles

2-Fluoroalkyl-substituted indole derivatives were simply prepared via the Grignard cyclization reaction (GCR) of corresponding fluorinated N-aryl imidoyl chlorides in good yields. This approach provides a novel and facile access to the biologically important 2-fluoroalkylindole derivatives.

Novel Heterocyclization of Imidoyl Chlorides with Mercaptocarboxylic Acids.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF.

Facile Synthesis of α‐Fluoro Substituted Amidines from Imidoyl Chlorides and Some of Its Application.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF.